CN103938180A - Preparation method of nanocarbon membrane with controllable thickness - Google Patents
Preparation method of nanocarbon membrane with controllable thickness Download PDFInfo
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- CN103938180A CN103938180A CN201410165434.7A CN201410165434A CN103938180A CN 103938180 A CN103938180 A CN 103938180A CN 201410165434 A CN201410165434 A CN 201410165434A CN 103938180 A CN103938180 A CN 103938180A
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Abstract
The invention provides a preparation method of a nanocarbon membrane with controllable thickness. The preparation method of the nanocarbon membrane with the controllable thickness comprises the steps that a substrate material is placed into a reaction cavity of molecular layer deposition equipment, high-purity nitrogen is used for purging, then a molecular layer deposition technology is adopted for depositing polyimide and diamine, and thermal treatment is carried out on polyimide grown on the substrate material in a reducing atmosphere, so that the carbon membrane is obtained. The preparation method of the nanocarbon membrane with the controllable thickness has the advantages of simple technology, easy operation and accurate and controllable thickness.
Description
Technical field
The invention belongs to a kind of preparation method of nano-carbon film, relate in particular to one and deposit by molecular layer the method that (MLD) technology is prepared the accurate controlled nano-carbon film of thickness.
Background technology
Carbon film has the plurality of advantages such as good conductivity, chemical stability are good, acid-alkali-corrosive-resisting, good biocompatibility, has important application in many fields such as catalysis, gas delivery, energy storage, wear-resistant coatings.The method that tradition is prepared carbon film can be divided into physical vapor deposition and chemical vapour deposition, as plasma enhanced chemical vapor deposition, pulsed laser deposition, magnetron sputtering, ion beam sputtering and liquid phase multiple adsorb-pyrolysis etc., these methods are difficult to accurately control thickness, also there is obvious limitation at aspects such as film uniformities, be conventionally applicable to the thicker film of growth.And physical vapor deposition and plasma enhanced chemical vapor deposition method are applicable to one side, non-omnidirectional surface deposition conventionally, can not sample surfaces is entirely coated, more inapplicable for vesicular structure.Traditional method is higher to requirement for experiment condition, experimental implementation is loaded down with trivial details.The patent of publication number CN103266306A has been set forth a kind of method of utilizing physical gas phase deposition technology to prepare ultrathin carbon films, deposit cavity vacuum tightness requires 0.5-1 Pa, substrate bias is at-200 V, anode layer ion source voltage is 300-500 V, experiment condition is comparatively harsh, relatively be applicable to generate flat film, inapplicable to complicated nano pore structure.The article of DOI:10.1039/c0cc05749e has been introduced a kind of method of the core-shell nano structure of preparing carbon coated with silver particle and has been studied its Raman reinforced effects.In the method, the silver sol of preparation is inserted in cetyl trimethylammonium bromide (CTAB) and adsorbed, then absorption is had the silver sol of CTAB to insert in the vitriol oil and carry out carbonization, repeat the process of absorption-carbonization, obtain the coated silver nano-grain of carbon.Very loaded down with trivial details on this process operation, and the thickness of carbon coating layer is also not easy to control.
Summary of the invention
In order to overcome the deficiency of above-mentioned traditional method, the object of the present invention is to provide the accurately preparation method of controlled nano-carbon film of simple, the easy to operate and thickness of a kind of technique.
Molecular layer deposition technique (MLD) is the extension of ald (ALD) technology, in the time that the film of deposition contains organic molecule (group), is just called molecular layer deposition.
Molecular layer deposition is a kind of advanced person's film deposition techniques, can be at even, the controlled film of the substrate material surface deposit thickness of various complexity, there is outstanding advantage compared with traditional method for manufacturing thin film.
Preparation method of the present invention comprises the steps:
(1) base material is put into the reaction chamber of molecular layer depositing device, purged 2-30min with high pure nitrogen, then start to deposit polyimide;
Molecular layer deposition technique (MLD) deposition parameter of setting is:
Temperature of reaction 100-200
oc;
Reaction source: adopting pyromellitic dianhydride (PMDA) and diamines is precursor, and PMDA source temperature is 130-180
oc; Diamines source temperature is in room temperature to 150
obetween C;
Carrier gas: 10-100 sccm high pure nitrogen;
Pulse, feel suffocated and purge time: first PMDA steam is sent into sediment chamber, burst length 0.1-30 s, BHT 3-60 s, purge time 5-90 s; Then diamines steam is sent into sediment chamber, burst length 0.01-10 s, BHT 3-60 s, purge time 5-90 s;
(2) polyimide obtaining growing on base material by molecular layer deposition technique in step (1) in reducing atmosphere at 400-1200
ounder C, thermal treatment 30-180 min, obtains carbon film.
Described base material is silicon chip, quartz glass plate, Copper Foil, porous alumina formwork, nano particle or nano wire etc. as mentioned above.
Diamines as above can be hexanediamine, Ursol D or 4,4'-diaminodiphenyl oxide etc.
Reducing atmosphere as above is H
2/ Ar reducing atmosphere.
The thickness of the carbon film as above obtaining can regulate by the frequency of depositing of polyimide.
Polyimide film thickness in heat treatment process of this MLD growth shrinks about 65-75% as mentioned above, and each MLD circulation makes the carbon film thickness obtaining increase to 0.05-0.50nm.
Carbon film prepared by the present invention is nitrogenous carbon film, and carbon film has uniform surface, and rootmean-square surfaceness only has 0.2-0.5 nm.Carbon film has good visible light permeability, and the visible light transmissivity of the carbon film that 10 deposition cycle obtain reaches more than 97%.
Preparation method of the present invention can carry out the coated of carbon film to the substrate of various complex topography.
The present invention is compared with existing carbon film technology of preparing, the invention has the advantages that: technique is simple, provide accurately controlled carbon film preparation method of a kind of thickness, and the carbon film good uniformity, the visible light permeability that obtain are high, have important potential application in photochemistry field.
Brief description of the drawings
Fig. 1 is the electromicroscopic photograph of the carbon film sample that obtains of embodiment 1.
Fig. 2 is the electromicroscopic photograph of the carbon film sample that obtains of embodiment 2.
Fig. 3 is the transmission electron microscope photo of the sample that obtains of embodiment 3.
Fig. 4 is the transmission electron microscope photo of the sample that obtains of embodiment 4.
Embodiment
Embodiment 1
The sediment chamber that single crystalline Si sheet is put into atomic shell conversion unit carries out the deposition of polyimide, and the deposition parameter of setting is: temperature of reaction is 130
oc, reaction source is PMDA and quadrol, PMDA source temperature is 140
oC, quadrol source temperature is room temperature.First purge 5 min with high pure nitrogen, then PMDA steam is sent into sediment chamber, the burst length is 1 s, and BHT is 5 s, and purge time is 10 s; Again quadrol steam is sent into sediment chamber, the burst length is 0.02 s, and BHT is 5 s, and purge time is 10 s, so far completes primary depositing circulation.Repeat deposition cycle 800 times.The Si sheet sample that growth is had to a polyimide is at 5% H
2in/Ar mixed atmosphere 500
oc thermal treatment 2 h, obtain carbon film sample.Analysis shows that sample is mainly undefined structure; Sample mainly contains C, O, N element, and the content that wherein content of C is 81.5%, N is 4.7%; Sample surfaces is very even, and rootmean-square surfaceness is 0.4 nm; Electromicroscopic photograph shows that the thickness of carbon film is 110 nm.
Embodiment 2
The sediment chamber that single crystalline Si sheet is put into atomic shell conversion unit carries out the deposition of polyimide, and the deposition parameter of setting is: temperature of reaction is 180
oc, reaction source is PMDA and hexanediamine, PMDA source temperature is 160
oC, hexanediamine source temperature is 50
oc.Purge 10 min with high pure nitrogen, then PMDA steam is sent into sediment chamber, the burst length is 5 s, and BHT is 15 s, and purge time is 30 s; Hexanediamine steam is sent into sediment chamber's (hexanediamine source temperature is), the burst length is 0.15 s again, and BHT is 15 s, and purge time is 30 s, so far completes primary depositing circulation.Repeat deposition cycle 200 times, obtain being grown in the Kapton on Si sheet.By sample at 10% H
2in/Ar mixed atmosphere 1000
oc reduces 1 h, obtains being grown in the carbon film sample on Si sheet.Analysis shows that sample is mainly undefined structure; Sample mainly contains C, O, N element, and the content that wherein content of C is 84.3%, N is 4.7%; Sample surfaces is very even, and rootmean-square surfaceness is 0.3 nm.Electromicroscopic photograph shows that the thickness of carbon film is 78 nm.
Embodiment 3
First by copper mesh (50 orders of buying; diameter 3.05 mm; Plano, Germany) aluminum oxide that deposits 30 circulations in atomic layer deposition apparatus protects, gold nano grain solution (50 nm that then 1 μ L bought; Strem Chemicals Inc.; Newburyport, MA, USA) drip on the copper mesh of aluminum oxide protection; naturally dry, copper mesh is put into the sediment chamber (160 of atomic layer deposition apparatus
oc), purge 20 min with high pure nitrogen, then PMDA steam is sent into sediment chamber, the burst length is 10 s, and BHT is 30 s, and purge time is 60 s; (Ursol D source temperature is 100 Ursol D steam to be sent into sediment chamber again
oc), the burst length is 2 s, and BHT is 30 s, and purge time is 60 s, so far completes primary depositing circulation.Repeat deposition cycle 20 times, obtain the coated gold nano grain sample of Kapton, by sample at 5% H
2in/Ar mixed atmosphere 600
oc reductase 12 h, obtains the gold nano grain sample of carbon film coated.Analysis shows that sample is mainly undefined structure.Transmission electron microscope photo shows that carbon film is coated on gold nano grain skin equably, and the thickness of coated carbon film is 1.4 nm.
Embodiment 4
The porous alumina formwork (channel diameter 200 nm) of buying is put into the sediment chamber (200 of atomic layer deposition apparatus
oc), purge 30 min with high pure nitrogen, then PMDA steam is sent into sediment chamber, the burst length is 20 s, and BHT is 60 s, and purge time is 90 s; (4,4'-diaminodiphenyl oxide source temperature is 150 4,4'-diaminodiphenyl oxide steam to be sent into sediment chamber again
oc), the burst length is 10 s, and BHT is 60 s, and purge time is 90 s, so far completes primary depositing circulation.Repeat deposition cycle 40 times, by the sample obtaining at 10% H
2in/Ar mixed atmosphere 1000
oc reduces 3 h, then this sample is put into the NaOH solution of 1M/L, leaves standstill 2 h to remove alumina formwork, obtains unsupported carbon nanotubes shape sample.Transmission electron microscope photo shows the even tube wall, smooth of this nanotube sample, and thickness is 15 nm.
Claims (7)
1. a preparation method for the controlled nano-carbon film of thickness, is characterized in that comprising the steps:
(1) base material is put into the reaction chamber of molecular layer depositing device, purged 2-30min with high pure nitrogen, then start to deposit polyimide;
In the molecular layer deposition technique of setting, deposition parameter is:
Temperature of reaction 100-200 oC;
Reaction source: adopting pyromellitic dianhydride and diamines is precursor, and pyromellitic dianhydride source temperature is 130-180 oC; Diamines source temperature in room temperature between 150 oC;
Carrier gas: 10-100 sccm high pure nitrogen;
Pulse, feel suffocated and purge time: first pyromellitic dianhydride steam is sent into sediment chamber, burst length 0.1-30 s, BHT 3-60 s, purge time 5-90 s; Then diamines steam is sent into sediment chamber, burst length 0.01-10 s, BHT 3-60 s, purge time 5-90 s;
(2) polyimide obtaining growing on base material by molecular layer deposition technique in step (1) in reducing atmosphere under 400-1200 oC thermal treatment 30-180 min, obtain carbon film.
2. the preparation method of the controlled nano-carbon film of a kind of thickness as claimed in claim 1, is characterized in that described base material is silicon chip, quartz glass plate, Copper Foil, porous alumina formwork, nano particle or nano wire.
3. the preparation of the controlled nano-carbon film of a kind of thickness as claimed in claim 1, is characterized in that described diamines is hexanediamine, Ursol D or 4,4'-diaminodiphenyl oxide.
4. the preparation method of the controlled nano-carbon film of a kind of thickness as claimed in claim 1, is characterized in that described reducing atmosphere is H
2with Ar mixed gas.
5. the preparation method of the controlled nano-carbon film of a kind of thickness as claimed in claim 1, is characterized in that the each molecular layer deposition cycle of described step (1) makes the carbon film thickness obtaining increase to 0.05-0.50nm.
6. the prepared product of preparation method of the controlled nano-carbon film of a kind of thickness as claimed in claim 1, is characterized in that the thickness of described carbon film regulates by the frequency of depositing of polyimide.
7. the prepared product of preparation method of the controlled nano-carbon film of a kind of thickness as claimed in claim 1, it is characterized in that carbon film is nitrogenous carbon film, carbon film rootmean-square surfaceness is 0.2-0.5 nm, and the visible light transmissivity of the carbon film that 10 deposition cycle obtain reaches more than 97%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111285686A (en) * | 2018-12-07 | 2020-06-16 | 南京动量材料科技有限公司 | Preparation process of composite porous carbon film and capacitor |
| CN113151801A (en) * | 2021-03-03 | 2021-07-23 | 电子科技大学 | Preparation method of self-supporting suspended carbon film |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101979315A (en) * | 2010-11-16 | 2011-02-23 | 中国科学院微电子研究所 | Preparation method of monoatomic-layer graphene film |
-
2014
- 2014-04-23 CN CN201410165434.7A patent/CN103938180A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101979315A (en) * | 2010-11-16 | 2011-02-23 | 中国科学院微电子研究所 | Preparation method of monoatomic-layer graphene film |
Non-Patent Citations (3)
| Title |
|---|
| MATTI PUTKONEN等: ""Atomic layer deposition of polyimide thin films"", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
| PENG YANG等: ""Uniform and Conformal Carbon Nanofilms Produced Based on Molecular Layer Deposition"", 《MATERIALS》 * |
| PENG YANG等: ""Uniform and Conformal Carbon Nanofilms Produced Based on Molecular Layer Deposition"", 《MATERIALS》, vol. 6, no. 27, 2 December 2013 (2013-12-02), pages 5602 - 5612 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111285686A (en) * | 2018-12-07 | 2020-06-16 | 南京动量材料科技有限公司 | Preparation process of composite porous carbon film and capacitor |
| CN113151801A (en) * | 2021-03-03 | 2021-07-23 | 电子科技大学 | Preparation method of self-supporting suspended carbon film |
| CN113151801B (en) * | 2021-03-03 | 2022-12-27 | 电子科技大学 | Preparation method of self-supporting suspended carbon film |
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Application publication date: 20140723 |